CN102923791B - Method for preparing multi-tunnel cobaltosic oxide flower-like microspheres by solvothermal method - Google Patents

Method for preparing multi-tunnel cobaltosic oxide flower-like microspheres by solvothermal method Download PDF

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Publication number
CN102923791B
CN102923791B CN201210419346.6A CN201210419346A CN102923791B CN 102923791 B CN102923791 B CN 102923791B CN 201210419346 A CN201210419346 A CN 201210419346A CN 102923791 B CN102923791 B CN 102923791B
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flower
solvothermal
cobaltosic oxide
jing
flakes
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CN102923791A (en
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施伟东
蒋金辉
张坤
孙绍芳
吴亚帆
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Jiangsu University
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Jiangsu University
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Abstract

The invention belongs to the technical field of nano-material synthesis, relates to a method for preparing microspheres having uniform morphology by a solvothermal method, and especially relates to a method for preparing multi-tunnel cobaltosic oxide flower-like microspheres by a solvothermal method. The method comprises the following steps of uniformly mixing cobalt nitrate, copper nitrate, ethylene glycol and ammonia water, transferring the mixture to a reactor with a Teflon lining, carrying out a high-temperature solvothermal reaction process, carrying out centrifugal separation, washing and vacuum drying of solvothermal reaction products, and carrying out calcination in a tubular furnace. The method utilizes ethylene glycol as a solvent and utilizes a solvothermal method to prepare a cobaltosic oxide material having a high yield and uniform morphology. The multi-tunnel cobaltosic oxide flower-like microspheres prepared by the method have good chemical stability and can be used for preparing an electrode material and a hydrogen production material of a storage battery. The method has simple processes and good reappearance and utilizes a cobalt inorganic compound as a cobalt source, wherein the cobalt inorganic compound has a low cost, can be acquired easily and satisfies environmental requirements. The method avoids pre-treatment processes such as aging, allows a low synthesis temperature, reduces energy consumption and a reaction cost, and is convenient for volume production.

Description

Solvent-thermal method is prepared the method for the flower-shaped microballoon of multi-pore channel tricobalt tetroxide
Technical field
The invention belongs to nano material synthesis technical field, relate to the method for utilizing solvent-thermal method to prepare pattern homogeneous microballoon, relate in particular to a kind of method that solvent-thermal method is prepared the flower-shaped microballoon of multi-pore channel tricobalt tetroxide.
Background technology
The structure and morphology of inorganic nano material and size regulation and control are attracting investigators' extensive concern always, and object is to make material property more excellent.In recent years, porous inorganic material is paid close attention to especially in investigation of materials, and this is mainly because it has potential application prospect in different fields.Nearest poroid material is applied to for study hotspot at the potential of field such as catalysis, sensor, fuel cell, super transmitter with it.As lithium ion battery, ion-exchange and catalytic process etc.There is the optical band gap of 2.4ev as the cobalt oxide (CoO) of important transition metal oxide semiconductor material, and optical band gap is at the Co of 1.48ev to 2.19ev 3o 4, because of the potential application of the aspects such as its material at sensor, heterogeneous catalysis, magneticsubstance, solar absorption, ultracapacitor, lithium ion battery, had in recent years research widely.Because its electrical capacity has higher theoretical value, the Co of nanostructure 3o 4be generally considered the electrode materials of lithium ion battery of future generation.Therefore, turn-around design and the nanostructure Co that synthesizes novel excellent performance of a large amount of research work 3o 4.Cobalt oxide is widely used catalyzed reaction, Li ionization cell, sensor and super capacitor field, the Co of various patterns 3o 4nano material is successfully synthesized out, comprises nano wire, nanometer rod, nanocubes, nanometer ball, nano flower and nanometer sheet.The synthetic method of report also has a lot, and image height temperature element directly synthesizes, microwave auxiliary reflux method, micro emulsion method, the hot method of solvent/water etc.
Until had the oxide compound of the desirable micro-nano cobalt of various synthetic different-shapes today.But the method for traditional synthetic three-dimensional structure material needs various templates, and these templates are not easy to remove, and this has had a strong impact on the performance of synthetic materials.Therefore, developing is easily very necessary by synthesize three-dimensional material without the method for template.But, develop that a kind of simple and reliable synthetic method is prepared with specific composition and the controlled poroid material of pattern remains very hang-up.
Summary of the invention
The object of the present invention is to provide the preparation method of the flower-shaped ball of tricobalt tetroxide that a kind of technique is simple, synthesis temperature is lower.
To achieve these goals, the technical solution used in the present invention is that Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, cupric nitrate, ethylene glycol and ammoniacal liquor are mixed and are transferred in teflon-lined reactor, after high-temperature solvent thermal response, will after the centrifugation of solvent thermal product, washing, vacuum-drying, in tube furnace, calcine and make.
Solvent-thermal method is prepared the method for the flower-shaped microballoon of multi-pore channel tricobalt tetroxide, comprises the steps:
Steps A, Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES and cupric nitrate are joined in ethylene glycol, mix;
Step B, add ammoniacal liquor again, stir into homogeneous mixture system;
Step C, mixed system is transferred in teflon-lined reactor, at 160 ~ 200 DEG C of constant temperature 12h, after naturally cooling, obtains solvent thermal product;
Step D, solvent thermal product obtained above is carried out to centrifugation, the solid product after centrifugal washs respectively 3 times with dehydrated alcohol and deionized water;
Step e, described solid product 60 ~ 80 DEG C of dry 6 ~ 12h in vacuum drying oven are obtained to precursor;
Step F, described precursor is placed in tube furnace with N 2protect 300～500 DEG C of calcining 3h.
In a preference of the present invention, described reactant is according to Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES: cupric nitrate: ethylene glycol: the ratio of ammoniacal liquor is that 2mol:0.5 ~ 1mol:35L:1 ~ 2L mixes.
In another preference of the present invention, in described step B, the weight percent concentration of ammoniacal liquor is 25 ~ 28wt%.
The reagent that the present invention participates in reaction is analytical pure, commercially available.
The flower-shaped microballoon of multi-pore channel tricobalt tetroxide making according to method disclosed by the invention, is to be 10 ~ 20nm by thickness the self-assembly of cobaltosic oxide nano sheet forms, and the diameter of flower-shaped microballoon is 0.8 ~ 1.2 micron.
Cobalt oxide (Co in the present invention 3o 4) structure determined by x-ray diffractometer, X-ray diffracting spectrum shows, the cobalt oxide (Co being prepared by liquid phase reaction and self-assembling technique combined technology 3o 4) be spinel structure, in collection of illustrative plates, there is no the peak of other material, illustrate that product is pure phase Co 3o 4.
Field emission scanning electron microscope test shows, the liquid phase reaction cobalt oxide (Co preparing that combines with self-assembling technique 3o 4) 0.8 ~ 1.2 micron of the diameter of flower-shaped ball, be to be 10 ~ 20nm by thickness nanometer sheet self-assembly forms.
beneficial effect
Spent glycol of the present invention (EG), as solvent, utilizes solvent process for thermosynthesizing to prepare the cobaltosic oxide nano material of the higher pattern homogeneous of productive rate, and this material has the advantages such as chemical stability is better, can be used for preparing electrode materials and the hydrogen manufacturing material of store battery.Technique of the present invention is simple, favorable reproducibility, and the mineral compound that cobalt used source is cobalt, cheap and easy to get, cost is low, Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES solubleness is high, meet environmental requirement, because the method does not need the pre-treatment of ageing and so on, synthesis temperature is lower, thereby reduce energy consumption and reaction cost, be convenient to batch production.
Brief description of the drawings
Fig. 1 embodiment 1 makes the X-ray diffracting spectrum (XRD) of the flower-shaped ball of tricobalt tetroxide micron.
Fig. 2 embodiment 1 makes the energy spectrogram (EDS) of the flower-shaped ball of tricobalt tetroxide micron.
Fig. 3 embodiment 1 makes the field emission scanning electron microscope figure (FESEM) of the flower-shaped ball of tricobalt tetroxide micron.
Embodiment
In order to understand better the present invention, further illustrate content of the present invention below in conjunction with embodiment, but content of the present invention is not only confined to the following examples.
embodiment 1
Tricobalt tetroxide (Co 3o 4) micron flower-shaped ball preparation process as follows:
A, 2mmol Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES will be entered in 35mlEG, in Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES: the ratio that cupric nitrate is 2:1 adds cupric nitrate, and the stirring continuing, until solution is even;
B, add again the ammoniacal liquor (25～28wt%) of 2ml, be stirred to evenly;
C, be transferred in teflon-lined reactor, constant temperature 12 hours at 180 DEG C, then naturally cooling, obtains hydrothermal product;
D, hydrothermal product obtained above is carried out to centrifugation, wash respectively 3 times with dehydrated alcohol and deionized water;
E, by the product after centrifugal in vacuum drying oven at 60 DEG C dry 12h obtain precursor;
F, precursor in tube furnace with N 2at doing to protect 500 DEG C, calcine 3h and obtain final product.
Co 3o 4the XRD of the flower-shaped ball product of micron is shown in Fig. 1, and Fig. 2 is shown in by EDS collection of illustrative plates, and the FESEM image of different-shape product is shown in Fig. 3.
In Fig. 1, the position of each diffraction peak and relative intensity all match with JCPDS card (42-1467), show that product is the Co of spinel 3o 4, in XRD figure spectrum, there is no other diffraction peak of mix, illustrate that the liquid phase-self-assembly method of the present invention's proposition is prepared Co 3o 4thing be pure mutually.
From Fig. 2, can find out that synthetic material is only containing aerobic and cobalt element by spectrogram.(copper exists as substrate, can get rid of from XRD analysis the existence of copper).
Tricobalt tetroxide (the Co preparing as can be seen from Figure 3 3o 4) the flower-shaped ball of micron is that the thin slice diameter that self-assembly forms that is about 10 ~ 20nm by thickness is 0.8 ~ 1.2 micron of microballoon.
embodiment 2
Tricobalt tetroxide (Co 3o 4) micron flower-shaped ball preparation process as follows:
A, 2mmol Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES will be entered in 35mlEG, in Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES: the ratio that cupric nitrate is 2:1 adds cupric nitrate, and the stirring continuing, until solution is even;
B, add again the ammoniacal liquor (25～28wt%) of 1ml, be stirred to evenly;
C, be transferred in teflon-lined reactor, at 180 DEG C of constant temperature 12h, then naturally cooling, obtains hydrothermal product;
D, hydrothermal product obtained above is carried out to centrifugation, wash respectively 3 times with dehydrated alcohol and deionized water;
E, the 60 DEG C of dry 12h in vacuum drying oven of the product after centrifugal are obtained to precursor;
F, precursor in tube furnace with N 2make 500 DEG C of calcining 3h of protection and obtain final product.
embodiment 3
Tricobalt tetroxide (Co 3o 4) micron flower-shaped ball preparation process as follows:
A, 2mmol Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES will be entered in 35mlEG, in Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES: the ratio that cupric nitrate is 2:1 adds cupric nitrate, and the stirring continuing, until solution is even;
B, add again the ammoniacal liquor (25～28wt%) of 2ml, be stirred to evenly;
C, be transferred in teflon-lined reactor, at 160 DEG C of constant temperature 12h, then naturally cooling, obtains hydrothermal product;
D, hydrothermal product obtained above is carried out to centrifugation, wash respectively 3 times with dehydrated alcohol and deionized water;
E, the 60 DEG C of dry 12h in vacuum drying oven of the product after centrifugal are obtained to precursor;
F, precursor in tube furnace with N 2make 500 DEG C of calcining 3h of protection and obtain final product.
embodiment 4
Tricobalt tetroxide (Co 3o 4) micron flower-shaped ball preparation process as follows:
A, 2mmol Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES will be entered in 35mlEG, in Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES: the ratio that cupric nitrate is 2:1 adds cupric nitrate, and the stirring continuing, until solution is even;
B, add again the ammoniacal liquor (25～28wt%) of 2ml, be stirred to evenly;
C, be transferred in teflon-lined reactor, at 200 DEG C of constant temperature 12h, then naturally cooling, obtains hydrothermal product;
D, hydrothermal product obtained above is carried out to centrifugation, wash respectively 3 times with dehydrated alcohol and deionized water;
E, the 60 DEG C of dry 12h in vacuum drying oven of the product after centrifugal are obtained to precursor;
F, precursor in tube furnace with N 2make 500 DEG C of calcining 3h of protection and obtain final product.
embodiment 5
Tricobalt tetroxide (Co 3o 4) micron flower-shaped ball preparation process as follows:
A, 2mmol Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES will be entered in 35mlEG, in Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES: the ratio that cupric nitrate is 2:1 adds cupric nitrate, and the stirring continuing, until solution is even;
B, add again the ammoniacal liquor (25wt%～28wt%) of 2ml, be stirred to evenly;
C, be transferred in teflon-lined reactor, constant temperature 12h at 200 DEG C of temperature, then naturally cooling, obtains hydrothermal product;
D, hydrothermal product obtained above is carried out to centrifugation, wash respectively 3 times with dehydrated alcohol and deionized water;
E, the 80 DEG C of dry 12h in vacuum drying oven of the product after centrifugal are obtained to precursor;
F, precursor in tube furnace with N 2make 500 DEG C of calcining 3h of protection and obtain final product.
embodiment 6
Tricobalt tetroxide (Co 3o 4) micron flower-shaped ball preparation process as follows:
A, 2mmol Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES will be entered in 35mlEG, in Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES: the ratio that cupric nitrate is 2:1 adds cupric nitrate, and the stirring continuing, until solution is even;
B, add again the ammoniacal liquor (25～28wt%) of 2ml, be stirred to evenly;
C, be transferred in teflon-lined reactor, at 180 DEG C of constant temperature 12h, then naturally cooling, obtains hydrothermal product;
D, hydrothermal product obtained above is carried out to centrifugation, wash respectively 3 times with dehydrated alcohol and deionized water;
E, the 80 DEG C of dry 6h in vacuum drying oven of the product after centrifugal are obtained to precursor;
F, precursor in tube furnace with N 2make 500 DEG C of calcining 3h of protection and obtain final product.
embodiment 7
Tricobalt tetroxide (Co 3o 4) micron flower-shaped ball preparation process as follows:
A, 2mmol Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES will be entered in 35mlEG, in Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES: the ratio that cupric nitrate is 2:1 adds cupric nitrate, and the stirring continuing, until solution is even;
B, add again the ammoniacal liquor (25～28wt%) of 2ml, be stirred to evenly;
C, be transferred in teflon-lined reactor, at 180 DEG C of constant temperature 12h, then naturally cooling, obtains hydrothermal product;
D, hydrothermal product obtained above is carried out to centrifugation, wash respectively 3 times with dehydrated alcohol and deionized water;
E, the 80 DEG C of dry 6h in vacuum drying oven of the product after centrifugal are obtained to precursor;
F, precursor in tube furnace with N 2make 300 DEG C of calcining 3h of protection and obtain final product.
embodiment 8
Tricobalt tetroxide (Co 3o 4) micron flower-shaped ball preparation process as follows:
A, 2mmol Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES will be entered in 35mlEG, in Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES: the ratio that cupric nitrate is 2:1 adds cupric nitrate, and the stirring continuing, until solution is even;
B, add again the ammoniacal liquor (25～28wt%) of 1ml, be stirred to evenly;
C, be transferred in teflon-lined reactor, at 180 DEG C of constant temperature 12h, then naturally cooling, obtains hydrothermal product;
D, hydrothermal product obtained above is carried out to centrifugation, wash respectively 3 times with dehydrated alcohol and deionized water;
E, the 60 DEG C of dry 6h in vacuum drying oven of the product after centrifugal are obtained to precursor;
F, precursor in tube furnace with N 2make 300 DEG C of calcining 3h of protection and obtain final product.
embodiment 9
Tricobalt tetroxide (Co 3o 4) micron flower-shaped ball preparation process as follows:
A, 2mmol Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES will be entered in 35mlEG, in Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES: the ratio that cupric nitrate is 2:1 adds cupric nitrate, and the stirring continuing, until solution is even;
B, add again the ammoniacal liquor (25～28wt%) of 1ml, be stirred to evenly;
C, be transferred in teflon-lined reactor, at 160 DEG C of constant temperature 12h, then naturally cooling, obtains hydrothermal product;
D, hydrothermal product obtained above is carried out to centrifugation, wash respectively 3 times with dehydrated alcohol and deionized water;
E, the 60 DEG C of dry 6h in vacuum drying oven of the product after centrifugal are obtained to precursor;
F, precursor in tube furnace with N 2make 300 DEG C of calcining 3h of protection and obtain final product.

Claims (3)

1. solvent-thermal method is prepared the method for the flower-shaped microballoon of multi-pore channel tricobalt tetroxide, it is characterized in that comprising the steps:
Steps A, Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES and cupric nitrate are joined in ethylene glycol, mix;
Step B, add ammoniacal liquor again, stir into homogeneous mixture system,
Described reactant is according to Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES: cupric nitrate: ethylene glycol: the ratio of ammoniacal liquor is that 2mol:0.5 ~ 1mol:35L:1 ~ 2L mixes,
The weight percent concentration of described ammoniacal liquor is 25～28wt%;
Step C, mixed system is transferred in teflon-lined reactor, at 160～200 DEG C of constant temperature 12h, after naturally cooling, obtains solvent thermal product;
Step D, solvent thermal product obtained above is carried out to centrifugation, the solid product after centrifugal washs respectively 3 times with dehydrated alcohol and deionized water;
Step e, described solid product 60～80 DEG C of dry 6 ~ 12h in vacuum drying oven are obtained to precursor;
Step F, described precursor is placed in tube furnace with N 2protect 300 ~ 500 DEG C of calcining 3h.
2. the flower-shaped microballoon of multi-pore channel tricobalt tetroxide making according to method described in claim 1, is characterized in that, the cobaltosic oxide nano sheet self-assembly that described flower-shaped microballoon is 10 ~ 20nm by thickness forms.
3. the flower-shaped microballoon of multi-pore channel tricobalt tetroxide according to claim 2, is characterized in that, the diameter of described flower-shaped microballoon is 0.8 ~ 1.2 micron.
CN201210419346.6A 2012-10-29 2012-10-29 Method for preparing multi-tunnel cobaltosic oxide flower-like microspheres by solvothermal method Expired - Fee Related CN102923791B (en)

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CN104787806B (en) * 2015-04-21 2016-07-06 济南大学 A kind of rose-shaped nano Cobalto-cobaltic oxide and preparation method thereof
CN106268814A (en) * 2015-05-20 2017-01-04 中国科学院大连化学物理研究所 A kind of flower-shaped Cobalto-cobaltic oxide catalyst and its preparation method and application
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